JP2678703B2 - Polymer scale anti-adhesion agent and method for producing polymer using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a scale adhesion inhibitor for polymerization of a monomer having an ethylenic double bond, a polymerization vessel, and a method for producing a polymer using the same.

[0002]

2. Description of the Related Art Conventionally, as a method for polymerizing vinyl monomers, suspension polymerization method, emulsion polymerization method, solution polymerization method, gas phase polymerization method,
Alternatively, a bulk polymerization method or the like is known. In any of these polymerization methods, the adhesion of the polymer scale is likely to occur at the site where the monomer contacts, such as the inner wall of the polymerization vessel and the stirring device.

[0003] When the polymer scale adheres, the yield of the polymer, the cooling capacity of the polymerization vessel and the like are reduced, and the scale is peeled and mixed into the product, resulting in a disadvantage that the quality of the product is lowered. In order to remove the adhered polymer scale, not only excessive labor and time are required,
Since unreacted monomers are included in this scale,
In recent years, there is a risk of human injury due to monomers (vinyl chloride and the like), which have become a very serious problem in recent years.

Conventionally, in order to prevent the adhesion of polymer scale to the inner wall of such a polymerization vessel, for example, as is practiced in the suspension polymerization of vinyl chloride, the polarity of amine compounds, quinone compounds, aldehyde compounds, etc. A method of applying an organic compound or a method of adding the compound to an aqueous medium is known (JP-B-45-30343). However, these methods show a scale prevention effect when the polymerization is repeated up to about 5 to 6 batches. However, when the number of polymerization batches is larger than that, the prevention effect is lost (poor in sustainability). . This point is particularly significant when a water-soluble catalyst is used, and is not industrially satisfactory.

In order to overcome this disadvantage, JP-A-60-30681
In the publication, a condensation product of an aromatic amine compound and an aromatic nitro compound is proposed. A coating film of a condensation product of this aromatic amine compound and an aromatic nitro compound,
When it is formed on the inner wall of the polymerization vessel where the monomer comes into contact, the scale does not adhere to the liquid phase portion inside the polymerization vessel even if the polymerization is repeated about 100 to 200 batches. Similarly, when a water-soluble catalyst is used, scale adhesion in the liquid phase is similarly prevented.

[0006]

However, there is a disadvantage that the scale adheres to the vicinity of the interface between the gas phase and the liquid phase located in the upper part of the polymerization vessel. Once the scale adheres near the interface between the gas phase and the liquid phase, the adhered scale gradually grows as the polymerization is repeated, and eventually peels off and may be mixed into the product polymer. . When the scale is mixed into the product polymer, when the product polymer is processed into a molded product such as a sheet, many fish eyes are generated in the molded product, and the quality of the molded product is significantly reduced. Will be lost.

When the product polymer is processed into a molded article such as a sheet, the resulting molded article is required to have high whiteness. That is, even if the polymer is molded into a sheet or the like without adding any coloring agent, the obtained molded product is slightly colored. This coloring is called initial coloring, and it is desired that the coloring be as small as possible. However, since the coating film consisting of the condensation product of the aromatic amine compound and the aromatic nitro compound may be peeled off or dissolved and mixed into the product polymer, the whiteness of the molded article is lowered, that is, the initial coloring. Sex deteriorates.

Therefore, an object of the present invention is to polymerize a monomer having an ethylenic double bond not only in the liquid phase part in the polymerization vessel but also in the vicinity of the interface between the gas phase part and the liquid phase part. In addition to effectively preventing the adhesion of polymer scale, when molded into a sheet, etc., a product polymer is obtained in which a molded product with extremely few fish eyes and good initial colorability is obtained. It is an object of the present invention to provide a polymer scale adhesion preventive agent and a method for producing a polymer using the preventive agent.

[0009]

Means for Solving the Problems In other words, the present invention achieves the above object by (A) methylene diamid
1, ethylenediamine, trimethylenediamine, 2,3
From diaminobutane and 2,4-diaminopentane
Polymer scale anti-adhesion agent for polymerization of monomer having ethylenic double bond, containing at least one aliphatic diamine compound selected from the group and a condensation compound of (B) quinone compound I will provide a.

Further, the present invention is a polymer producing method according to polymerization in a polymerization vessel a monomer having an e ethylenic double bond, to the inner wall surface, in the polymerization vessel having the coating film, There is provided a production method which comprises the step of carrying out the above-mentioned polymerization, thereby preventing adhesion of polymer scale.

The condensation product, which is an essential component of the polymer scale inhibitor of the present invention, is a substance obtained by condensing the specific (A) aliphatic diamine compound and (B) quinone compound. . Hereinafter, the raw materials and the synthesis will be described.

(A) Aliphatic Diamine Compound The aliphatic diamine compound (A) used in the present invention is methylenediamine, ethylenediamine, trimethylenediamine, 2,3-diaminobutane, 2,4. -Diaminopentane. In the present invention, the above aliphatic diamine compounds can be used alone or as a mixture of two or more kinds.

(B) Quinone Compound The quinone compound (B) is represented by, for example, the following general formula (1)
It is a compound represented by (4).

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[Here, R ¹ is --H, --NH ₂ , --Cl,-
_{Br, -OH, -NO 2, -COCH} 3, - OCH 3, -N (CH 3) 2
Or represents an alkyl group having 1 to 3 carbon atoms, R ² is-
It represents _{H, -NH 2, -OH, -CH} 3, -COOH, and -SO ₃ H. Specific examples include ortho or para-benzoquinone, oxy-para-benzoquinone, chloro-para-benzoquinone, bromo-para-benzoquinone, juroquinone, chloranil and the like. Among these, preferable are ortho-benzoquinone, para-benzoquinone, oxy-para-benzoquinone and duroquinone.

Embedded image

Embedded image [Here, R ¹ and R ² may be the same or different,
As described above. R ³ is -H, -OH, -C
_{H 3, -Cl, -COCH 3,} - OCH 3, -COOH, represents a -SO ₃ H. ]

Specific examples include 6-methyl-1,4-naphthoquinone, 2-methyl-1,4-naphthoquinone, lawson, juglone, plumbagin, α-naphthoquinone and β-naphthoquinone. Preferred of these are:
Lawson, Huglon, Plumbagin, α-naphthoquinone. In the present invention, the quinone compound may be used alone or as a mixture of two or more kinds.

Condensation reaction Aliphatic diamine compound (A) and quinone compound described above
The condensation of (B) is carried out in an organic solvent medium, if necessary, in the presence of a condensation catalyst. The pH of the organic solvent medium is usually in the range of 1-13. The pH adjuster can be used without particular restrictions.

As a medium for the condensation reaction, an organic solvent type medium is used. Here, the organic solvent-based medium refers to an organic solvent and a mixed solvent of the organic solvent and water (water having a content of 30% by weight or less). Examples of the organic solvent include alcohols such as methanol, ethanol and propanol; ketones such as acetone and methyl ethyl ketone; and esters such as methyl acetate and ethyl acetate. Of these, alcohols are preferred.

If necessary, a condensation catalyst is used. Examples of the condensation catalyst include oxyacids such as iodic acid, periodate, potassium periodate, sodium perchlorate, and oxyacid salts; hydrogen peroxide. , Peroxides such as sodium peroxide, potassium persulfate, ammonium persulfate; iodine, bromine,
Chlorine and fluorine halogens, ferrous chloride, ferric chloride,
Metal salts such as copper sulfate and cuprous chloride; organic peroxides such as benzoyl peroxide, peracetic acid, cumene hydroperoxide, perbenzoic acid, para-menthane hydroperoxide; α, α′-azobisisobutyrate Ronitrile,
Azo catalysts such as α, α'-azobis-2,4-dimethylvaleronitrile, nitrobenzene, ortho, meta or para-oxynitrobenzene, ortho, meta or para-nitroanisole, ortho, meta or para-chloronitrobenzene, ortho, Aromatic nitro compounds such as meta or para-nitrobenzoic acid, ortho, meta or para-nitrobenzenesulfonic acid, etc. are exemplified. Since the quinone compound acts as a condensation catalyst, the condensation reaction is performed without using a condensation catalyst.

At least one of the aliphatic diamine compounds (A)
One or more and at least one or more of the quinone compound (B),
A condensation product is obtained by reacting in the above-mentioned organic solvent medium, if necessary, under a condensation catalyst, usually at room temperature to 200 ° C. for 0.5 to 100 hours.

Aliphatic diamine compound for carrying out condensation reaction
The ratio of (A) and quinone compound (B) is influenced by the aliphatic diamine compound, the type of quinone compound and the solvent used, the reaction temperature, the reaction time, etc. The quinone compound (B) is preferably 0.01 to 15 parts by weight, more preferably 0.05 to 3.0 parts by weight, per part. If the amount of the quinone compound (B) is too large or too small, the effect of preventing scale attachment of the condensation product obtained will be reduced. The polymer scale adhesion preventive agent of the present invention having the above condensation product as an essential component, for example, is formed as a coating film on the inner wall surface of the polymerization vessel or the like to prevent the adhesion of the polymer scale to the inner wall surface of the polymerization vessel or the like. To prevent. Usually, when forming the coating film on the inner wall surface of the polymerization vessel,
The polymer scale anti-adhesion agent is in the form of a solution or dispersion,
That is, it is used as a coating liquid.

Preparation of Coating Liquid The coating liquid containing the condensation product produced by the above condensation reaction may be prepared, for example, by adding the following solvent to the condensation product containing solution which has undergone the above condensation reaction. . Also,
After removing the solvent of the condensation product-containing solution, pulverizing and adding the following solvent, or by pouring the condensation product-containing solution into cold water to precipitate the condensation product, the precipitate is filtered off, It may be prepared by adding the following solvent to the dried product. As the solvent used for preparing the coating solution of the scale inhibitor of the condensation product of the component (A) and the component (B),
For example, water; methanol, ethanol, propanol, butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 3-methyl-1.
Alcohol solvents such as butanol, 2-methyl-2-butanol and 2-pentanol; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone;
Ester solvents such as methyl formate, ethyl formate, methyl acetate, methyl acetoacetate; ether solvents such as 4-methyldioxolan, ethylene glycol diethyl ether;
Furans; aprotic solvents such as dimethylformamide, dimethylsulfoxide, acetonitrile and the like. These are used singly or as a mixture of two or more solvents.

The pH of the coating solution is preferably 3.0 to 13.0, particularly preferably 8.0 to 13.0. The pH adjuster can be used without particular limitation, and examples thereof include phosphoric acid, perchloric acid, sulfuric acid, hydrochloric acid, nitric acid, phytic acid, acetic acid,
Acidic compounds such as paratoluene sulfonic acid, tannic acid,
LiOH, KOH, NaOH, Na ₂ CO ₃ , Na ₂ SiO ₃ , Na ₂ HPO
₄ , alkali metal compounds such as NH ₄ OH or ammonium compounds, ethylenediamine, tetramethylenediamine,
Examples thereof include alkaline compounds such as ethanolamine, diethanolamine, triethanolamine, guanidine, diethylenediamine, and triethylenetetramine. The concentration of the condensation product of the component (A) and the component (B) in the coating liquid is
As long as the total coating amount described below can be obtained, it is not particularly limited,
Usually about 0.001 to 15% by weight, preferably 0.01 to 1% by weight
It is.

Further, for example, cationic, nonionic and anionic surfactants can be added to the coating solution as long as they do not impair the scale preventive action, and if necessary, hydroxyl group-containing polymer. Water-soluble polymers such as compounds, cationic polymer compounds, anionic polymer compounds and amphoteric polymer compounds can be added.

Examples of the hydroxyl group-containing polymer compound include starches such as amylose, amylopectin, dextrin, oxidized starch, acetyl starch, nitro starch, methyl starch, carboxymethyl starch and derivatives thereof; pectic acid, protopectin, Hydroxyl group-containing vegetable slime such as pectinic acid, alginic acid, laminarin, fucoidin, agar, carrageenin; hydroxyl-containing animal slime such as hyaluronic acid, chondroitin sulfate, heparin, keratosulfate, chitin, chitosan, caronin sulfate, limacoitin sulfate;
Nucleic acids such as ribonucleic acid and deoxyribonucleic acid; methyl cellulose, ethyl cellulose, carboxymethyl cellulose,
Glycol cellulose, benzyl cellulose, cyanoethyl cellulose, methylene ether of cellulose, triphenylmethyl cellulose, formyl cellulose, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose sulfonate, cellulose carbamate, nitrocellulose, phosphorus Cellulose derivatives such as acid cellulose and cellulose xanthate; hemicelluloses such as xylan, mannan, alabogalactan, galactan, and araban; alcohol lignin, dioxane lignin, phenol lignin, hydrotrovic lignin, mercapto lignin, thioglycolic acid lignin, Lignin sulfonic acid, alkali lignin, thioalkali lignin, acid lignin, oxidation - Ammonia lignin, such as periodate lignin; phenol - formaldehyde resins, partially saponified polyvinyl alcohol, polyvinyl alcohol and the like.

Examples of the cationic polymer compound include polyvinylamine, polyethyleneamine, polyethyleneimine, polyacrylamide, N-vinyl-2-pyrrolidone-acrylamide copolymer, cyclized polymer of dimethyldiamyl ammonium chloride, and dimethyl. Cyclic polymer of diethylammonium bromide, cyclized polymer of diallylamine hydrochloride, cyclized copolymer of dimethyldiallyl ammonium chloride and sulfur dioxide, polyvinyl pyridine, polyvinyl pyrrolidone, polyvinyl carbazole, polyvinyl imidazoline, polydimethylaminoethyl acrylate , Polydimethylaminoethylmethacrylate, polydiethylaminoethylacrylate, polydiethylaminoethylmethacrylate, etc. have a nitrogen atom in the side chain and Atoms cationic polyelectrolyte bearing a charged positively, and the like.

Examples of the amphoteric polymer compound include amphoteric polymer compounds such as glue, gelatin, casein and albumin. As the anionic polymer compound,
For example, sulfomethylated polyacrylamide; polyacrylic acid; alginic acid, acrylamide-vinyl sulfonic acid copolymer, polymethacrylic acid, polystyrene sulfonic acid and the like, or alkali metal salts or ammonium salts thereof; Anionic polymer compounds having a carboxyl group or a sulfonic acid group are exemplified.

Further, an inorganic compound may be appropriately added to the coating solution, if necessary, as long as it does not impair the scale preventing action. Examples of inorganic compounds that can be added include orthosilicic acid, metasilicic acid, mesodisilicic acid, mesotrisilicic acid, mesotetrasilicic acid, sodium metasilicate, sodium orthosilicate, sodium disilicate, sodium tetrasilicate, and water glass. Silicic acids or silicates; oxyacid salts of metals selected from alkaline earth metals such as magnesium, calcium and barium; zinc group metals such as zinc; aluminum group metals such as aluminum; platinum group metals such as platinum; Metal salts such as salts, nitrates, hydroxides and halides; and inorganic colloids such as ferric hydroxide colloid, silicate colloid, barium sulfate colloid and aluminum hydroxide colloid. The above-mentioned inorganic colloid may be prepared by, for example, mechanical pulverization, irradiation of ultrasonic waves, electric dispersion and chemical methods.

Formation of Coating Film To form a coating film on the inner wall surface of the polymerization vessel using the coating solution prepared as described above, first, the coating solution is applied to the inner wall surface of the polymerization vessel, and then, for example, at room temperature. After thoroughly drying in the temperature range from 1 to 100 ° C, further wash with water if necessary.

Further, it is preferable that the coating solution is applied not only to the inner wall surface of the polymerization vessel, but also to other portions where the monomer contacts during the polymerization. For example, stirring blades, stirring shafts, baffles,
Examples include capacitors, headers, search coils, bolts and nuts. More preferably, even if the coating liquid is other than the part where the monomer comes into contact during polymerization, there is a possibility that the polymer scale may adhere thereto, for example, the inner surface of equipment and piping of a recovery system for unreacted monomer. For example, it is better to form the coating film. Specifically, monomer distillation tower, condenser,
Inner surfaces such as monomer storage tanks and valves.

In this way, when a coating film is formed on the site where the monomer contacts during the polymerization and the site where the other polymer scale may adhere, the adhesion of the polymer scale to those sites. Is prevented. The method of applying the coating solution to the inner wall surface of the polymerization vessel is not particularly limited. Examples thereof include brush coating, spray coating, a method in which the polymerization vessel is filled with the coating solution and then withdrawn, and other methods described in JP-A-57-61001.
Nos. 55-36288, 56-501116, 56-50
No. 1117, JP-A-59-11303 and the like can also be used.

The method of drying the wet surface by applying the coating solution is not limited, and the following method can be used, for example. That is, after the application of the coating solution, a method in which warm air of an appropriate temperature is applied to the application surface, or the inner wall surface of the polymerization vessel to which the coating solution is to be applied and other surfaces are previously heated to, for example, 30 to 80 ° C. For example, a method of directly applying a coating solution to the heated surface can be used. After the application surface is dried, the application surface is washed with water as needed.

The coating film thus obtained has a total coating amount after drying of usually 0.001 g / m ² or more, particularly 0.05 to ²
g / m ² . The above coating operation is performed by
It may be carried out for every 10 to several dozen batches of polymerization. Since the formed coating film has high durability and maintains the action of preventing the adhesion of the polymer scale, it is not always necessary to perform the coating for each batch of polymerization. For this reason, the productivity of the product polymer is improved.

Polymerization As described above, a coating film is formed by applying a coating treatment to the inner wall of the polymerization vessel, and preferably to other portions where the monomer contacts during the polymerization, and then the coating is formed in the polymerization vessel by a conventional method. Polymerize. That is, in addition to a monomer having an ethylenic double bond and a polymerization initiator (catalyst), if necessary, a polymerization medium such as water and a suspending agent, a solid dispersant, a nonionic, anionic emulsifier, etc. A dispersant or the like is charged, and then polymerization is performed by a conventional method.

Examples of the monomer having an ethylenic double bond which is polymerized by applying the method of the present invention include vinyl halides such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; acrylic acid. , Methacrylic acid, and their esters or salts; maleic acid, fumaric acid, and their esters or anhydrides; diene-based monomers such as butadiene, chloroprene, isoprene; styrene, acrylonitrile, vinylidene halide, vinyl ether, etc. To be

The type of polymerization to which the method of the present invention is applied is not particularly limited, and suspension polymerization, emulsion polymerization, solution polymerization,
It is effective in any polymerization mode of bulk polymerization and gas phase polymerization, and is particularly suitable for polymerization in an aqueous medium such as suspension polymerization and emulsion polymerization.

The general polymerization method will be specifically described below by taking the cases of suspension polymerization and emulsion polymerization as examples. First,
Water and a dispersant are charged into a polymerization vessel, and then a polymerization initiator is charged. Next, the inside of the polymerization vessel was evacuated to reduce the pressure to 0.1 to 760 mmHg, and then the monomer was charged (at this time, the internal pressure of the polymerization vessel was
Usually 0.5 ~ 30kgf / cm ²・ G), then 30 ~ 150
Polymerizes at a reaction temperature of ° C. During the polymerization, if necessary,
One or more of water, a dispersant and a polymerization initiator are added. In addition, the reaction temperature during the polymerization differs depending on the type of the monomer to be polymerized, for example, in the case of vinyl chloride polymerization.
Polymerization is carried out at 30-80 ° C, and 50-
The polymerization is carried out at 150 ° C. In the polymerization, the internal pressure of the polymerization vessel is 0 to 7 kgf /
cm ² · G, or when the difference between the inlet and outlet temperatures of the cooling water flowing into and out of the jacket provided around the polymerization vessel has almost disappeared (that is, when the heat generated by the polymerization reaction has disappeared). ), It is determined that the process is completed. Water, dispersant, and polymerization initiator charged during the polymerization are usually 20 to 500 parts by weight of water, 0.01 to 30 parts by weight of a dispersant, 0.01 to 5 parts by weight of a polymerization initiator based on 100 parts by weight of a monomer. Department.

In the case of solution polymerization, an organic solvent such as toluene, xylene or pyridine is used as a polymerization medium instead of water. A dispersant is used as needed. Other polymerization conditions are generally the same as the polymerization conditions for suspension polymerization and emulsion polymerization. In addition, in the case of bulk polymerization, after evacuating the inside of the polymerization vessel to a pressure of about 0.01 to 760 mmHg, charging the monomer and the polymerization initiator into the polymerization vessel,
Polymerizes at a reaction temperature of -10 to 250 ° C. For example, the polymerization is carried out at 30 to 80 ° C. for the polymerization of vinyl chloride, and at 50 to 150 ° C. for the polymerization of styrene.

When the polymer scale adhesion preventing method of the present invention is applied to carry out the polymerization, the polymer scale adhesion can be prevented regardless of the material of the inner wall surface of the polymerization vessel. The adhesion of polymer scale can be prevented even when the polymerization is carried out in a steel or other steel-made polymerization vessel, a glass-lined polymerization vessel, or the like.

What is added to the polymerization system can be used without any restrictions. That is, for example, t-butyl peroxy neodecanoate, bis (2-ethylhexyl) peroxy dicarbonate, 3,5,5-trimethylhexanoyl peroxide, α-cumyl peroxy neodecanoate, cumene hydroper Oxide, cyclohexanone peroxide, t-butylperoxypivalate, bis (2-ethoxyethyl) peroxydicarbonate, benzoyl peroxide, lauroyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropylperoxydicarbonate , Α,
polymerization initiators such as α'-azobisisobutyronitrile, α, α'-azobis-2,4-dimethylvaleronitrile, potassium peroxodisulfate, ammonium peroxodisulfate, p-menthane hydroperoxide; partially saponified polyvinyl Suspending agents such as alcohols, polyacrylic acid, copolymers of vinyl acetate and maleic anhydride, cellulose derivatives such as hydroxypropylmethylcellulose, natural or synthetic polymer compounds such as gelatin; solid dispersants such as calcium phosphate and hydroxyapatite; Nonionic emulsifiers such as sorbitan monolaurate, sorbitan triolate and polyoxyethylene alkyl ether; sodium alkylbenzenesulfonate such as sodium lauryl sulfate and sodium dodecylbenzenesulfonate; sodium dioctylsulfosuccinate Anionic emulsifiers such as lium; fillers such as calcium carbonate and titanium oxide; stabilizers such as tribasic lead sulfate, calcium stearate, dibutyltin dilaurate, dioctyltin mercaptide; lubricants such as rice wax, stearic acid, cetyl alcohol; D
OP: plasticizer such as DBP; mercaptans such as t-dodecyl mercaptan; chain transfer agents such as trichloroethylene; pH
Even in a polymerization system in which a regulator or the like is present, the method of the present invention can effectively prevent the adhesion of polymer scale.

The polymer scale anti-adhesion agent of the present invention may be used for forming a coating film on the inner wall surface of the polymerization vessel or the like, and may be further added directly to the polymerization system to improve the scale prevention effect. You can also let it. In this case, the amount of the polymer scale adhesion inhibitor is suitably about 10 to 1000 ppm based on the total weight of the monomers to be charged. At the time of addition, care should be taken not to affect the quality of the product polymer such as fish eye, bulk specific gravity, particle size distribution and the like.

[0041]

EXAMPLES Production Example 1 Production of Condensation Product No. 1 A reactor equipped with a condenser was charged with 990 g of methanol and 7 g of para-benzoquinone as a quinone compound and stirred at room temperature to dissolve para-benzoquinone in methanol. Next, 3 g of ethylenediamine as an aliphatic diamine compound was added to the above methanol solution and the temperature was raised to 50 ° C. After reacting at 50 ° C. for 10 hours, it was cooled to obtain a solution of a condensation product. This solution was designated as condensation product No. 1.

Condensation product No. 2 to 15 using the quinone compound and the solvent such as the aliphatic diamine compounds shown in Table 1 at the reaction temperature and the reaction time shown in the table. A condensation reaction was carried out in the same manner as in Example 1. 2 to 15 were obtained. However, the experiment No. marked with * in Table 1 was used. 2 , 3 , and 10 to 15 are comparative examples.

[0043]

[Table 1]

Example 1 (Experiment Nos. 101 to 115 ) Polymerization was carried out in the following manner using a stainless steel polymerization vessel equipped with a stirrer and having an internal volume of 2000 liters. The condensation products used in each experiment are shown in Table 2. First, after adding a solvent to the condensation product so that the solvent ratio and the concentration of the condensation product are as shown in Table 2, the pH adjustment shown in Table 2 is performed to adjust the pH shown in Table 2. A coating solution was prepared by adding the agent. These coating solutions are applied to the inner wall of the polymerization vessel, the stirring shaft, the stirring blade, and other portions where the monomers come into contact with each other during the polymerization.
After heating and drying at 15 ° C. for 15 minutes to form a coating film, it was washed with water.

However, in Experiment No. 2 marked with * in Table 2.
102 and 103, (A), Ri Comparative Example der coated a coating solution containing only one component of the component (B), also
Experiment No. marked with *. 110 to 115 are different from the present invention
Coating solution using an aliphatic diamine compound etc.
Comparative Example der Ru.

Thereafter, 800 kg of water, 400 kg of vinyl chloride, 500 g of partially saponified polyvinyl alcohol, 50 g of hydroxypropyl methylcellulose and 50 g of 3,5,5-trimethylhexahexylate were placed in the polymerization vessel where the coating film was formed by the coating treatment as described above. Charge 140 g of Noyl peroxide and stir it.
Polymerization was carried out at 66 ° C for 6 hours. After completion of the polymerization, the produced polymer and unreacted monomer were recovered, and the inside of the polymerization vessel was washed with water to remove the residual resin.

The operation from the formation of the coating film to the washing of the inner wall of the polymerization vessel as described above is defined as one batch, and the same operation is repeated 10 batches thereafter, and the scale deposition in the polymerization vessel of the 10th batch is performed. The amount was examined in two parts, the liquid phase part and the vicinity of the interface between the gas phase part and the liquid phase part. After scraping off the scale adhering to the predetermined area of 10 x 10 cm of each part with a spatula, weigh the scale and multiply the measured value by 100 to 1 m.
The scale adhesion amount per ² was determined. Table 2 shows the results. In addition, the fish eyes when the polymer obtained in each experiment was formed into a sheet were measured by the following method. Table 2 shows the results.

Measurement of fish eye A mixture prepared by mixing 100 parts by weight of polymer, 50 parts by weight of DOP, 1 part by weight of dibutyltin dilaurate, 1 part by weight of cetyl alcohol, 0.25 part by weight of titanium oxide and 0.05 part by weight of carbon black. Using a 6-inch roll at 150 ° C for 7
After kneading for minutes, the sheet was formed into a sheet having a thickness of 0.2 mm, and the number of fish eyes contained per 100 cm ^{2 of the} obtained sheet was examined by a light transmission method. Further, the brightness index (L value) when the polymer obtained in each experiment was molded into a sheet was measured by the following method. Table 2 shows the results.

Measurement of lightness index (L value) 100 parts by weight of the obtained polymer, a stabilizer (TS manufactured by Akishima Chemical Co., Ltd., TS
-101) 1 part by weight, stabilizer (C-100J, manufactured by Katsuta Kako Co., Ltd.)
0.5 parts by weight and 50 parts by weight of dioctyl phthalate as a plasticizer are kneaded in a two-roll mill at 160 ° C. for 5 minutes, and then formed into a sheet having a thickness of 1 mm. Next, put the formed sheet in a 4 × 4 × 1.5 cm formwork, 160 ° C, 65-70 kgf / cm
^2. Heat and press mold for 0.2 hours to prepare a sample for measurement. For this sample, the lightness index L in the color difference formula of Hunter described in JIS Z 8730 (1980) was determined, and it was evaluated that the larger the L value, the higher the whiteness, that is, the better the initial coloring property.

The L value is obtained as follows. JIS Z 8722
The stimulus value Y of the XYZ colorimetric system is obtained by a stimulus value direct reading method using a standard light C and a photoelectric colorimeter (Z-1001DP colorimetric colorimeter manufactured by Nippon Denshoku Industries Co., Ltd.) according to the description. As the geometrical conditions for illumination and light reception, condition d described in JIS Z 8722, section 4.3.1 was adopted. From the obtained stimulus value Y,
The L value is calculated from the equation described in JIS Z 8730 (1980): L = 10Y1 ^{/ 2} .

[0051]

[Table 2]

Example 2 (Experiment Nos. 201 to 209 ) Polymerization was carried out as follows using a stainless steel polymerization vessel equipped with a stirrer and having an internal volume of 20 liters. In each experiment,
The condensation products used are shown in Table 3. First, after adding a solvent so that the solvent ratio, the concentration, and the concentration of the condensation product shown in Table 3 are obtained, the pH adjusting agent shown in Table 3 is added to adjust the pH shown in Table 3 and then applied. A liquid was prepared. These coating solutions are applied to the inner wall of the polymerization vessel, the stirring shaft, the stirring blade, and other portions where the monomers come into contact with each other during the polymerization, and heated at 50 ° C for 15 minutes
After drying to form a coating film, it was washed with water. However, * in Table 3
Experiment No. marked. 202 and 203 are (A),
It is a comparative example in which a coating liquid containing only one of the components (B) was applied.

Next, 9 kg of water and sodium dodecylbenzenesulfonate 2 were placed in the coating vessel thus coated.
After 25 g, 12 g of t-dodecyl mercaptan and 13 g of potassium peroxodisulfate were charged and replaced with nitrogen gas, 1.3 kg of styrene and 3.8 kg of butadiene were charged and polymerized at 50 ° C. for 20 hours. After completion of the polymerization, the produced polymer and unreacted monomer were recovered, and the inside of the polymerization vessel was washed with water to remove the residual resin.

Then, the operation from the formation of the above coating film to the washing of the inner wall of the polymerization vessel through the polymerization is regarded as one batch, and the same operation is repeated 10 batches thereafter, and the scale adhesion in the polymerization vessel of the 10th batch is repeated. The amount was examined in the same manner as in Example 1 for two parts, the liquid phase part and the vicinity of the interface between the gas phase part and the liquid phase part. Table 3 shows the results. Further, the brightness index (L value) when the polymer obtained in each experiment was molded into a sheet was measured by the following method. Table 3 shows the results.

Measurement of lightness index (L value) To 1 kg of the obtained polymer was added 1 kg of a 2% magnesium sulfate solution.
, And the precipitate is filtered off. The precipitate separated by filtration was washed with hot water at 80 to 90 ° C. two to three times,
The resin was dried at 40 ° C. for 25 hours using a vacuum dryer.
Put the resin obtained in a 9 × 9 cm, 0.1 cm thick mold,
5 ° C., and heated at 50 to 60 kgf / cm ² 0.2 hours, the final pressure 80kg
A sample for measurement is prepared by pressure molding at f / cm ² . For this sample, the lightness index L value was determined in the same manner as described above.

[0056]

[Table 3]

[0057]

According to the present invention, the adhesion of polymer scale can be effectively prevented not only in the liquid phase part in the polymerization vessel but also in the vicinity of the interface between the gas phase part and the liquid phase part. The resulting product polymer has significantly less fish eyes after molding. Furthermore, since the coating film formed on the inner wall of the polymerization vessel according to the present invention does not peel off during the polymerization or dissolve in the polymerization system, the whiteness after molding of the product polymer is high, and the initial coloring is performed. The properties are good.

Further, when the polymerization is carried out by applying the present invention, it is not necessary to carry out the work of removing the polymer scale for each polymerization, thereby improving the productivity.

Claims (2)

(57) [Claims] 1. (A) Methylenediamine, ethylenediami
Amine, trimethylenediamine, 2,3-diaminobutane and
And 2,4-diaminopentane selected from the group consisting of
A polymer scale anti-adhesion agent for polymerization of a monomer having an ethylenic double bond, containing at least one aliphatic diamine compound and a condensation compound of (B) a quinone compound. 2. The method according to claim 1, wherein the monomer having an ethylenic double bond is
A method for producing a polymer by polymerization in a reactor, wherein the (A) component and (B) according to claim 1 are provided on the inner wall of the reactor.
In a polymerization vessel having a coating containing the condensation product of the components,
The method has the step of carrying out the above-mentioned polymerization.
A manufacturing method in which the adherence of particles is prevented.